US3700587A - Silicone oil antifoam - Google Patents

Silicone oil antifoam Download PDF

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US3700587A
US3700587A US119756A US3700587DA US3700587A US 3700587 A US3700587 A US 3700587A US 119756 A US119756 A US 119756A US 3700587D A US3700587D A US 3700587DA US 3700587 A US3700587 A US 3700587A
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stocks
silicone oil
delayed coking
centistoke
oil antifoam
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US119756A
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James A Hyde
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ChampionX LLC
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Nalco Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material

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  • TEST PROCEDURE l A test tube is charged with grams of coker feedstock. This sample is heated to 850 F. and maintained at that temperature for the evaluation in order to simulate the conditions of a coking drum.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Silicon Polymers (AREA)

Abstract

THE FOAMING OCCAISONED BY THE CONVERSION OF RESIDUAL PETROLEUM STOCKS INTO COKE BY DELAYED COKING PROCESS IS CONTROLLED BY TREATING SUCH STOCKS WITH A POLYDIMETHYL SIOLOXANE WHICH HAS A CENTISTOKE VISCOSITY OF AT LEAST 150,000.

Description

Oct. 24, 1972 J. A. HYDE SILICONE OIL ANTIFOAM 3 Sheets-Sheet 1 Filed March 1, 1971 ANTIFOAM ACTIVITY OF DIFFERENT VISCOSITY SILICONES Silicone dose of .4ppm
60,000 cstk. Silicone x Silicone dilution of ltol [50,000 cstK. SaliconeA l o e od n .80 3
m w h Q 5 A 3 mfitu 2 Z- kt mt SE0.
o TIME IN SECONDS secono 00 SE OF $lLlCONE- Oct. 24, 1972 J. A. HYDE SILICONE OIL ANTIFOAM Filed March 1, 1971 3 Sheets-Sheet 2 ANTI FOAM ACTIVITY OF DIFFERENT VlSCOSITY SILICONES FIG I AS A FUNCTION OFTIME 150.000 csfk. snucone A SlLlCONE DOSE os=.24 PPm 400,000 cs'bK SlLlCONE 0 mucous DILUTIONOF.
l'l'o 250 MWtUrZ ktmzmrt ITO.
TIME IN SECONDS FIRST DOSE OF SILJCONE FIG.11A
o a r .m 0 Em Mn 8 v A n s n I e m I O. I J v w L 1 4 w O l I I I N S 2; A 2 E E I! s an m D O D E //,U,, M m 4 T a a o s A I. 7 6 5 A. 3 7- .wwtus lctmiwt $33k 3 Sheets-Sheet" 5 Filed March 1. 1971 ANTIFOAM ACTIVITY OF DIFFERENT VISCOSITY SILICONES A5 A FUNCTION OF TIME 5 I 0 mm a p m w n o d m w e e n n m 0 MM 0 1. I 5 $3 I I OX U O m w M 4 o O o c c c UH... 9 5 in w. kk k 3 C C C I an O O O r 1 M Q. m A w 1 I I m n o m Qui F. M6225 ZIIQEE v5.6a
TIME IN SECONDS FI RST DOSE OF SILICON o 5 .t onH 7e n VA s m m a q o J A s 1 0 n 4 N o Owm 3 I 4/ r wa 4 WW I \fi J o D J E A? mm I T- /r f 7 ...I 6 5 4 3 2 hmtvg 5 klmlwb Z101 United States Patent Int. Cl. Cg 9/14 US. Cl. 208-131 2 Claims ABSTRACT OF THE DISCLOSURE The foaming occasioned by the conversion of residual petroleum stocks into coke by delayed coking processes is controlled by treating such stocks with a polydimethyl siloxane which has a centistoke viscosity of at least 150,000.
In the processing of various residual petroleum stocks into coke, a commonly used technique is the well-known delayed coking process. In the delayed coking process heavy residual oils are heated to above 500 C. by pumping them at high velocity through a pipe furnace and then changing these oils to an insulated coking drum. This process is further described in the Encyclopedia of Chemical Technology, 2nd edition, volume IV.
The delayed coking process produces quantities of foam which is undesirable since it diminishes the eflicient operation of the process. To control foam in the delayed coking process it is customary to treat the stocks while being processed with polydimethyl siloxane polymers.
The polydimethyl siloxane polymers most commonly used as defoamers in this application are of relatively low molecular weight as evidence by their centistoke viscosities. Typical polydimethyl siloxanes have centistoke viscosities of about 12,500. In a few cases polydimethyl siloxanes have been used which have centistoke viscosities of about 60,000.
The present invention is directed to provide improved defoaming methods for the treatment of petroleum stocks which are subjected to delayed coking processes.
In accordance with the invention it has been found that the foaming of residual petroleum stocks subjected to delayed coking processes may be inhibited by treating said stocks with from 0.05 up to about 100 ppm. of a polydimethyl siloxane which has a centistoke viscosity of at least 150,000. In a preferred embodiment of the invention it is preferred to use polydimethylsiloxanes which have centistoke viscosities ranging between 400,000 to 3,000,000, which are applied in a preferred dosage range of from 0.1 to 10 p.p.m.
To use these viscous polydimethyl siloxanes it is de- 3,700,587 Patented Oct. 24, 1972 ice sirable that they be first dispersed in petroleum hydrocarbon solvents such as kerosenes, naphthas, aromatic oils and the like. In some cases it is desirable to blend oil soluble surfactants with the polydimethyl siloxanes and the petroleum hydrocarbon liquid.
To illustrate the advantages and merits of the invention reference may be had to the drawings, e.g. FIGS. I, II and III, which show the relative merits of the polydimethyl siloxanes used in this invention over other lower molecular weight materials.
The data shown in the FIGS. I, I I and III were based upon the following test procedure:
TEST PROCEDURE l) A test tube is charged with grams of coker feedstock. This sample is heated to 850 F. and maintained at that temperature for the evaluation in order to simulate the conditions of a coking drum.
(2) For the evaluation, different viscosity silicones were diluted with deordorized kerosene. This evaluation was made on a straight weight basis.
(3) The diluted silicone is added one drop at a time.
(4) The foam height is recorded before and immediately after the silicone is added and every 10 seconds thereafter.
(5) When the foam height has reached /2 inch below the initial height, the next drop of antifoam is added. This procedure is continued until 3 drops have been added.
I claim:
1. A method of inhibiting foaming of residual petroleum stocks during their conversion into coke by a delayed coking process which comprises treating said residual petroleum stocks with from 0.05 up to about ppm. of a polydimethyl siloxane which has a centistoke viscosity of at least 150,000.
2. The method of claim 1 where the polydimethyl siloxane has a centistoke viscosity of from 400,000 to 3,000,000 and it is used as a dosage ranging from 0.1 to 10 ppm.
References Cited UNITED STATES PATENTS 2,702,793 2/ 1955 Smith 25278 3,235,502 2/1966 Waldmann 25249.6 3,383,327 5/1968 Sullivan 252358 JAMES E. POER, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R.
US119756A 1971-03-01 1971-03-01 Silicone oil antifoam Expired - Lifetime US3700587A (en)

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082690A (en) * 1977-02-07 1978-04-04 Dow Corning Corporation Antifoam process for non-aqueous systems
US4176047A (en) * 1978-04-10 1979-11-27 Continental Oil Company Removal of organic compounds from coker gasoline
US4257778A (en) * 1979-07-31 1981-03-24 Nihon Kogyo Kabushiki Kaisha Process for producing synthetic coking coal of high volatile matter content
FR2492677A1 (en) * 1980-10-28 1982-04-30 Nl Industries Inc Foam inhibition in delayed coking - using higher aliphatic alcohol
US4329528A (en) * 1980-12-01 1982-05-11 General Electric Company Method of defoaming crude hydrocarbon stocks with fluorosilicone compounds
US4396495A (en) * 1982-01-25 1983-08-02 Uop Inc. Reduction of foaming in a slurry catalyst hydrocarbon conversion process
US4557737A (en) * 1983-04-05 1985-12-10 The British Petroleum Company P.L.C Oil gas separation
US4596653A (en) * 1983-10-21 1986-06-24 The British Petroleum Company P.L.C. Demulsifying process
US4612109A (en) * 1980-10-28 1986-09-16 Nl Industries, Inc. Method for controlling foaming in delayed coking processes
US4645587A (en) * 1984-12-07 1987-02-24 Union Oil Company Of California Process for removing silicon compounds from hydrocarbon streams
US4711714A (en) * 1984-06-30 1987-12-08 The British Petroleum Company P.L.C. Method for the separation of gas from oil
US4961840A (en) * 1989-04-13 1990-10-09 Amoco Corporation Antifoam process for delayed coking
US4969988A (en) * 1988-04-15 1990-11-13 Petro-Canada Inc. Antifoam to achieve high conversion in hydroconversion of heavy oils
US5667669A (en) * 1996-03-22 1997-09-16 Betzdearborn Inc. Methods for inhibiting foam
EP0916377A2 (en) * 1997-11-14 1999-05-19 Dow Corning S.A. Foam control compositions
US6083998A (en) * 1998-04-24 2000-07-04 Betzdearborn Inc. Defoamer and methods of use thereof
US20050042166A1 (en) * 2001-03-06 2005-02-24 Kindig James Kelly Method for the production of hydrogen-containing gaseous mixtures
WO2005051512A1 (en) 2003-11-25 2005-06-09 Baker Hugues Incorporated Silicone defoamer to better control hydrocarbon foam and reduce silicon content of liquid hydrocarbon products
US20110284425A1 (en) * 2004-12-06 2011-11-24 The University Of Wyoming Research Corporation D/B/A Western Research Institute Hydrocarbonaceous Material Upgrading Method
CN103768831A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 High temperature stable defoaming agent and application thereof in delay coking
ES2531588R1 (en) * 2012-03-19 2015-05-13 Foster Wheeler Usa Corporation METHOD FOR REDUCING THE USE OF SILICONE ANTI-PUMP IN DELAYED COQUIZATION PROCESSES
CN106512487A (en) * 2016-11-02 2017-03-22 佛山迅拓奥科技有限公司 4-amino-2-sodium hydroxybenzoate synergistic polysiloxane defoaming agent

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082690A (en) * 1977-02-07 1978-04-04 Dow Corning Corporation Antifoam process for non-aqueous systems
US4176047A (en) * 1978-04-10 1979-11-27 Continental Oil Company Removal of organic compounds from coker gasoline
US4257778A (en) * 1979-07-31 1981-03-24 Nihon Kogyo Kabushiki Kaisha Process for producing synthetic coking coal of high volatile matter content
US4612109A (en) * 1980-10-28 1986-09-16 Nl Industries, Inc. Method for controlling foaming in delayed coking processes
FR2492677A1 (en) * 1980-10-28 1982-04-30 Nl Industries Inc Foam inhibition in delayed coking - using higher aliphatic alcohol
US4329528A (en) * 1980-12-01 1982-05-11 General Electric Company Method of defoaming crude hydrocarbon stocks with fluorosilicone compounds
US4396495A (en) * 1982-01-25 1983-08-02 Uop Inc. Reduction of foaming in a slurry catalyst hydrocarbon conversion process
US4557737A (en) * 1983-04-05 1985-12-10 The British Petroleum Company P.L.C Oil gas separation
US4596653A (en) * 1983-10-21 1986-06-24 The British Petroleum Company P.L.C. Demulsifying process
US4711714A (en) * 1984-06-30 1987-12-08 The British Petroleum Company P.L.C. Method for the separation of gas from oil
US4645587A (en) * 1984-12-07 1987-02-24 Union Oil Company Of California Process for removing silicon compounds from hydrocarbon streams
US4969988A (en) * 1988-04-15 1990-11-13 Petro-Canada Inc. Antifoam to achieve high conversion in hydroconversion of heavy oils
US4961840A (en) * 1989-04-13 1990-10-09 Amoco Corporation Antifoam process for delayed coking
US5667669A (en) * 1996-03-22 1997-09-16 Betzdearborn Inc. Methods for inhibiting foam
EP0916377A2 (en) * 1997-11-14 1999-05-19 Dow Corning S.A. Foam control compositions
EP0916377A3 (en) * 1997-11-14 1999-06-16 Dow Corning S.A. Foam control compositions
US6083998A (en) * 1998-04-24 2000-07-04 Betzdearborn Inc. Defoamer and methods of use thereof
US6448298B1 (en) 1998-04-24 2002-09-10 Betzdearborn, Inc. Defoamer and methods of use thereof
US20050042166A1 (en) * 2001-03-06 2005-02-24 Kindig James Kelly Method for the production of hydrogen-containing gaseous mixtures
WO2005051512A1 (en) 2003-11-25 2005-06-09 Baker Hugues Incorporated Silicone defoamer to better control hydrocarbon foam and reduce silicon content of liquid hydrocarbon products
US9045699B2 (en) * 2004-12-06 2015-06-02 The University Of Wyoming Research Corporation Hydrocarbonaceous material upgrading method
US20110284425A1 (en) * 2004-12-06 2011-11-24 The University Of Wyoming Research Corporation D/B/A Western Research Institute Hydrocarbonaceous Material Upgrading Method
ES2531588R1 (en) * 2012-03-19 2015-05-13 Foster Wheeler Usa Corporation METHOD FOR REDUCING THE USE OF SILICONE ANTI-PUMP IN DELAYED COQUIZATION PROCESSES
RU2629945C2 (en) * 2012-03-19 2017-09-05 ФОСТЕР ВИЛЕР ЮЭсЭй КОРПОРЕЙШН Method to reduce consumption of silicone de-foaming agents in delayed coking processes
CN103768831A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 High temperature stable defoaming agent and application thereof in delay coking
CN103768831B (en) * 2012-10-24 2015-05-13 中国石油化工股份有限公司 High temperature stable defoaming agent and application thereof in delay coking
CN106512487A (en) * 2016-11-02 2017-03-22 佛山迅拓奥科技有限公司 4-amino-2-sodium hydroxybenzoate synergistic polysiloxane defoaming agent
CN106512487B (en) * 2016-11-02 2018-07-27 江门市冠达化工科技有限公司 A kind of polysiloxane-based antifoaming agent of 4- amino-2-hydroxybenzoic acids sodium synergy

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